The invention relates to novel substituted p-trifluoromethylphenyluracils, to a process for their preparation and to their use as herbicides.
It is known that certain substituted p-trifluoromethylphenyluracils, such as, for example, the compound 3-(3-chloro-4-trifluoromethyl-phenyl)-6-(2,6-difluoro-phenyl)-[1H,3H]-pyrimidine-2,4-dione, have pesticidal properties, i.e. they are active against certain animal pests, in particular against insects and mites (cf. JP 05025142xe2x80x94cited in Chem. Abstracts 119:117269). However, nothing has yet been disclosed about a herbicidal activity of these compounds.
This invention, accordingly, provides the novel substituted p-trifluoromethylphenyluracils of the general formula (I) 
in which
R1 represents hydrogen, cyano or halogen,
R2 represents the grouping A1xe2x80x94A2xe2x80x94A3 in which
A1 represents a single bond, represents O, S, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylsulphonyl or arylsulphonyl,
A1 furthermore represents alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, each of which is optionally substituted by halogen,
A2 represents a single bond, represents O, S, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A413  in which A4 represents hydrogen, hydroxyl, alkyl, alkoxy, aryl, alkylsulphonyl or arylsulphonyl,
A2 furthermore represents alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, each of which is optionally substituted by halogen,
A3 represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyanato, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chorosulphonyl, halogen, represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl, each of which is optionally substituted by halogen or alkoxy, represents alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl, each of which is optionally substituted by halogen, represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl, each of which is optionally substituted by halogen, cyano, carboxyl, alkyl and/or alkoxy-carbonyl, or represents aryl, aryloxy, aralkyl, arylalkoxy, aryloxycarbonyl or arylalkoxycarbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, halogen, alkyl, halogenoalkyl, alkyloxy, halogenoalkyloxy and/or alkoxy-carbonyl,
A3 furthermore represents in each case optionally fully or partially hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylalkyl, furylalkyl, thienylalkyl, oxazolylalkyl, isoxazolalkyl, thiazolalkyl, pyridinylalkyl, pyrimidinylalkyl, pyrazolylalkoxy, furylalkoxy, represents perhydropyranylalkoxy or pyridylalkoxy,
R3 represents hydrogen, halogen or optionally halogen-substituted alkyl,
R4 represents optionally halogen-substituted alkyl, and
R5 represents hydrogen, amino or optionally hydroxyl-, cyano-, halogen- or alkoxy-substituted alkyl.
The novel substituted p-trifluoromethylphenyluracils of the general formula (I) are obtained when
aminoalkenoic esters of the general formula (II) 
in which
R3 and R4 are each as defined above and
R represents alkyl, aryl or arylalkyl
are reacted with p-trifluoromethylphenyl isocyanates of the general formula (III) 
in which
R1 and R2 are each as defined above
or with p-trifluoromethylphenylurathanes (p-trifluoromethylphenylcarbamates) of the general formula (IV) 
in which
R1 and R2 are each as defined above and
R represents alkyl, aryl or arylalkyl,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
and, if appropriate, further conversions within the scope of the above definitions of substituents are carried out by customary methods on the resulting compounds of the formula (I).
The compounds of the general formula (I) can be converted by customary methods into other compounds of the general formula (I) according to the above definitions of substituents, for example by customary electrophilic or nucleophilic substitution reactions (for example R2: Fxe2x86x92OH, SH, NH2, OCH3, SC2H5, NHC3H7, NHSO2CH3; R5: HNH2, CH3)xe2x80x94cf. also the preparation examples.
The novel substituted p-trifluoromethylphenyluracils of the general formula (I) have strong herbicidal activity. Additionally, they are well tolerated by important crop plants, such as, for example, wheat, barley and maize.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinylxe2x80x94also in combination with heteroatom""s, such as in alkoxy or alkylthioxe2x80x94are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which
R1 represents hydrogen, cyano, fluorine, chlorine or bromine,
R2 represents the grouping A1xe2x80x94A2xe2x80x94A3 in which
A1 represents a single bond, represents O, S, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl,
A1 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine or chlorine,
A2 represents a single bond, represents O, S, xe2x80x94SOxe2x80x94, SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulphonyl or phenylsulphonyl,
A2 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, each of which is optionally substituted by fluorine or chlorine,
A3 represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyanato, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, halogen, represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups and being in each case optionally substituted by fluorine, chlorine, bromine or C1-C4-alkoxy, represents alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and being in each case optionally substituted by fluorine, chlorine or bromine, represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups and being in each case optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkyl and/or C1-C4-alkoxy-carbonyl, or represents phenyl, phenyloxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenyloxycarbonyl or phenyl-C1-C4-alkoxycarbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyloxy, C1-C4-halogenoalkyloxy and/or C1-C4-alkoxy-carbonyl, represents (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C1-C4-alkyl, furyl-C1-C4-alkyl, thienyl-C1-C4-alkyl, oxazolyl -C1-C4-alkyl, isoxazole-C1-C4-alkyl, thiazole-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy, furylmethoxy, represents perhydropyranylmethoxy or pyridylmethoxy,
R3 represents hydrogen, fluorine, chlorine, bromine or optionally fluorine- and/or chlorine-substituted alkyl having 1 to 4 carbon atoms,
R4 represents optionally fluorine- and/or chlorine-substituted alkyl having 1 to 4 carbon atoms, and
R5 represents hydrogen, amino or optionally hydroxyl-, cyano-, fluorine-, chlorine- or C1-C4-alkoxy-substituted alkyl having 1 to 4 carbon atoms.
The invention in particular relates to compounds of the formula (I) in which
R1 represents hydrogen, fluorine or chlorine,
R2 represents the grouping A1xe2x80x94A2xe2x80x94A3 in which
A1 represents a single bond, represents O, S, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl or ethylsulphonyl,
A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl or propine-1,3-diyl,
A2 represents a single bond, represents O, S, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94 in which A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl or phenylsulphonyl,
A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl or propine-1,3-diyl,
A3 represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulpho, fluorine, chlorine, bromine, represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, represents propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, each of which is optionally substituted by fluorine or chlorine, represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo-propylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, each of which is optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, or represents phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl, each of which is optionally substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl, represents (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl, methyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolemethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy,
R3 represents, hydrogen, fluorine, chlorine, bromine or in each case optionally fluorine- and/or chlorine-substituted methyl or ethyl,
R4 represents in each case fluorine- and/or chlorine-substituted methyl or ethyl, and
R5 represents hydrogen, amino or in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl or ethyl.
The general or preferred radical definitions given above apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other as desired, that is to say combinations between the stated ranges of preferred compounds are also possible.
Examples of compounds of the formula (1) according to the invention are listed in the groups below.
Group I 
R2 has, for example, the meanings given in the list below:
hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, fluoroethyl, chloroethyl, chlorofluoroethyl, difluoroethyl, dichloroethyl, trifluoroethyl, trichloroethyl, chlorodifluoroethyl, tetrafluoroethyl, chlorotrifluoroethyl, pentafluoroethyl, fluoropropyl, chloropropyl, difluoropropyl, dichloropropyl, trifluoropropyl, cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl, propoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylpropyl, propoxycarbonylpropyl, 1-propen-3-yl (allyl), 3-methyl-1-propen-3-yl, 2-buten-4-yl (crotonyl), 1-propin-3-yl (propargyl), 3-methyl-1-propin-3-yl, 2-butin-4-yl, cyclopropyl, cyanocyclopropyl, carboxycyclopropyl, difluorocyclopropyl, dichlorocyclopropyl, methylcyclopropyl, methoxycarbonylcyclopropyl, ethoxycarbonylcyclopropyl, cyclobutyl, cyanocyclobutyl, carboxycyclobutyl, difluorocyclobutyl, trifluorocyclobutyl, tetrafluorocyclobutyl, chlorotrifluorocyclobutyl, methylcyclobutyl, cyclopentyl, cyanocyclopentyl, carboxycyclopentyl, fluorocyclopentyl, chlorocyclopentyl, difluorocyclopentyl, dichlorocyclopentyl, methylcyclopentyl, methoxycarbonylcyclopentyl, ethoxycarbonylcyclopentyl, cyclohexyl, cyanocyclohexyl, carboxycyclohexyl, fluorocyclohexyl, chlorocyclohexyl, difluorocyclohexyl, dichlorocyclohexyl, methylcyclohexyl, trifluoromethylcyclohexyl, methoxycarbonylcyclohexyl, ethoxycarbonylcyclohexyl, cyclopropylmethyl, difluorocyclopropylmethyl, dichlorocyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyanocyclohexylmethyl, carboxycyclohexylmethyl, fluorocyclohexylmethyl, chlorocyclohexylmethyl, methylcyclohexylmethyl, trifluoromethylcyclohexylmethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy, fluoroethoxy, chloroethoxy, chlorofluoroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, trichloroethoxy, chlorodifluoroethoxy, tetrafluoroethoxy, chlorotrifluoroethoxy, pentafluoroethoxy, fluoropropoxy, chloropropoxy, difluoropropoxy, dichloropropoxy, trifluoropropoxy, cyanomethoxy, cyanoethoxy, cyanopropoxy, cyanobutoxy, carboxymethoxy, carboxyethoxy, carboxypropoxy, carboxybutoxy, methoxymethoxy, ethoxymethoxy, propoxymethoxy, methoxyethoxy, ethoxyethoxy, propoxyethoxy, methoxypropoxy, ethoxypropoxy, propoxypropoxy, methoxycarbonylmethoxy, ethoxycarbonylmethoxy, propoxycarbonylmethoxy, methoxycarbonylethoxy, ethoxycarbonylethoxy, propoxycarbonylethoxy, methoxycarbonylpropoxy, ethoxycarbonylpropoxy, propoxycarbonylpropoxy, 1-propen-3-yl-oxy(allyloxy), 3-methyl-1-propen-3-yl-oxy, 2-buten-4-yl-oxy (crotonyloxy), 1-propin-3-yl -oxy(propargyloxy), 3-methyl-1-propin-3-yl-oxy, 2-butin-4-yl-oxy, cyclopropyloxy, cyanocyclopropyloxy, carboxycyclopropyloxy, difluorocyclopropyloxy, dichlorocyclopropyloxy, methylcyclopropyloxy, methoxycarbonylcyclopropyloxy, ethoxycarbonylcyclopropyloxy, cyclobutyloxy, cyanocyclobutyloxy, carboxycyclobutyloxy, difluorocyclobutyloxy, trifluorocyclobutyloxy, tetrafluorocyclobutyloxy, chlorotrifluorocyclobutyloxy, methylcyclobutyloxy, cyclopentyloxy, cyanocyclopentyloxy, carboxycyclopentyloxy, fluorocyclopentyloxy, chlorocyclopentyloxy, difluorocyclopentyloxy, dichlorocyclopentyloxy, methylcyclopentyloxy, methoxycarbonylcyclopentyloxy, ethoxycarbonylcyclopentyloxy, cyclohexyloxy, cyanocyclohexyloxy, carboxycyclohexyloxy, fluorocyclohexyloxy, chlorocyclohexyloxy, difluorocyclohexyloxy, dichlorocyclohexyloxy, methylcyclohexyloxy, trifluoromethylcyclohexyloxy, methoxycarbonylcyclohexyloxy, ethoxycarbonylcyclohexyloxy, cyclopropylmethoxy, difluorocyclopropylmethoxy, dichlorocyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyanocyclohexylmethoxy, carboxycyclohexylmethoxy, fluorocyclohexylmethoxy, chlorocyclo-hexylmethoxy, methylcyclohexylmethoxy, trifluoromethylcyclohexylmethoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, n-, i-, s- or t-pentylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, fluorodichloromethylthio, fiuoroethylthio, chloroethylthio, chlorofluoroethylthio, difluoroethylthio, dichloroethylthio, trifluoroethylthio, trichloroethylthio, chlorodifluoroethylthio, tetrafluoroethylthio, chlorotrifluoroethylthio, pentafluoroethylthio, fluoropropylthio, chloropropylthio, difluoropropylthio, dichloropropylthio, trifluoropropylthio, cyanomethylthio, cyanoethylthio, cyanopropylthio, cyanobutylthio, carboxymethylthio, carboxyethylthio, carboxypropylthio, carboxybutylthio, methoxycarbonylmethylthio, ethoxycarbonylmethylthio, propoxycarbonylmethylthio, methoxycarbonylethylthio, ethoxycarbonylethylthio, propoxycarbonylethylthio, methoxycarbonylpropylthio, ethoxycarbonylpropylthio, propoxycarbonylpropylthio, 1-propen-3-yl-thio(allylthio), 3-methyl-1-propen-3-yl-thio, 2-buten-4-yl-thio, 1-propin-3-yl-thio (propargylthio), 3-methyl-1-propin-3-yl-thio, 2-butin-4-yl-thio, cyclopropylthio, cyanocyclopropylthio, carboxycyclopropylthio, difluorocyclopropylthio, dichlorocyclopropylthio, methylcyclopropylthio, methoxycarbonylcyclopropylthio, ethoxycarbonylcyclopropylthio, cyclobutylthio, cyanocyclobutylthio, carboxycyclobutylthio, difluorocyclobutylthio, trifluorocyclobutylthio, tetrafluorocyclobutylthio, chlorotrifluorocyclobutylthio, methylcyclobutylthio, cyclopentylthio, cyanocyclopentylthio, carboxycyclopentylthio, fluorocyclopentylthio, chlorocyclopentylthio, difluorocyclopentylthio, dichlorocyclopentylthio, methylcyclopentylthio, methoxycarbonylcyclopentylthio, ethoxycarbonylcyclopentylthio, cyclohexylthio, cyanocyclohexylthio, carboxycyclohexylthio, fluorocyclohexylthio, chlorocyclohexylthio, difluorocyclohexylthio, dichlorocyclohexylthio, methylcyclohexylthio, trifluoromethylcyclohexylthio, methoxycarbonylcyclohexylthio, ethoxycarbonylcyclohexylthio, cyclopropylmethylthio, difluorocyclopropylmethylthio, dichlorocyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyanocyclohexylmethylthio, carboxycyclohexylmethylthio, fluorocyclohexylmethylthio, chlorocyclohexylmethylthio, methylcyclohexylmethylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, n-, i-, s- or t-pentylamino, cyanomethylamino, cyanoethylamino, cyanopropylamino, cyanobutylamino, carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxybutylamino, methoxymethylamino, ethoxymethylamino, propoxymethylamino, methoxyethylamino, ethoxyethylamino, propoxyethylamino, methoxypropylamino, ethoxypropylamino, propoxypropylamino, methoxycarbonylmethylamino, ethoxycarbonylmethyamino, propoxycarbonylmethylamino, methoxycarbonylethylamino, ethoxycarbonylethylamino, propoxycarbonylethylamino, methoxycarbonylpropyamino, ethoxycarbonylpropyamino, propoxycarbonylpropylamino, 1-propen-3-yl-amino(allylamino), 3-methyl-1-propen-3-ylamino, -2-buten-4-yl-amino(crotonylamino), 1-propin-3-yl-amino(propargylamino), 3-methyl-1-propin-3-yl-amino, 2-butin-4-yl-amino, cyclopropylamino, cyanocyclopropylamino, carboxycyclopropylamino, difluorocyclopropylamino, dichlorolcyclopropylamino, methylcycopropylamino, methoxycarbonylcyclopropylamino, ethoxycarbonylcyclopropylamino, cyclobutylamino, cyanocyclobutylamino, carboxycyclobutylamino, difluorocyclobutylamino, trifluorocyclobutylamino, tetrafluorocyclobutylamino, chlorotrifluorocyclobutylamino, methylcyclobutylamino, cyclopentylamino, cyanocyclopentylamino, carboxycyclopentylamino, fluorocyclopentylamino, chlorocyclopentylamino, difluorocyclopentylamino, dichlorocyclopentylamino, methylcyclopentylamino, methoxycarbonylcyclopentylamino,ethoxycarbonylcyclopentylamino, cyclohexylamino, cyanocyclohexylamino, carboxycyclohexylamino, fluorocyclohexylamino, chlorocyclohexylamino, difluorocyclohexylamino, dichlorocyclohexylamino, methylcyclohexylamino, trifluoromethylcyclohexylamino, methoxycarbonylcyclohexylamino, ethoxycarbonylcyclohexylamino, cyclopropylmethylamino, difluorocyclopropylmethylamino, dichlorocyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino, cyclohexylmethylamino, cyanocyclohexylmethylamino, carboxycyclohexylmethylamino, fluorocyclohexylmethylamino, chlorocyclohexylmethylamino, methylcyclohexylmethylamino, trifluoromethylcyclohexylmethylamino, phenyl, cyanophenyl, carboxyphenyl, nitrophenyl, fluorophenyl, chlorophenyl, bromophenyl, methylphenyl, trifluoromethylphenyl, methoxyphenyl, difluoromethoxyphenyl, trifluoromethoxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, benzyl, cyanobenzyl, carboxybenzyl, fluorobenzyl, chlorobenzyl, methylbenzyl, trifluoromethylbenzyl, methoxybenzyl, difluoromethoxybenzyl, trifluoromethoxybenzyl, methoxycarbonylbenzyl, ethoxycarbonylbenzyl, phenylethyl, furyl, furylmethyl, tetrahydrofuryl, tetrahydrofurylmethyl, thienyl, tetrahydrothienyl, oxetanyl, oxazolyl, isoxazolyl, phenoxy, cyanophenoxy, carboxyphenoxy, nitrophenoxy, fluorophenoxy, chlorophenoxy, bromophenoxy, methylphenoxy, trifluoromethylphenoxy, methoxyphenoxy, difluoromethoxyphenoxy, trifluoromethoxyphenoxy, methoxycarbonylphenoxy, ethoxycarbonylphenoxy, benzyloxy, cyanobenzyloxy, carboxybenzyloxy, fluorobenzyloxy, chlorobenzyloxy, methylbenzyloxy, trifluoromethylbenzyloxy, methoxybenzyloxy, difluoromethoxybenzyloxy, trifluoromethoxybenzyloxy, methoxycarbonylbenzyloxy, ethoxycarbonylbenzyloxy, phenylethoxy, furyloxy, furylmethoxy, tetrahydrofuryloxy, tetrahydrofurylmethoxy, thienyloxy, tetrahydrothienyloxy, oxetanyloxy, oxazolyloxy, isoxazolyloxy, phenylthio, cyanophenylthio, carboxyphenylthio, nitrophenylthio, fluorophenylthio, chlorophenylthio, bromophenylthio, methylphenylthio, trifluoromethylphenylthio, methoxyphenylthio, difluoromethoxyphenylthio, trifluoromethoxyphenylthio, methoxycarbonylphenylthio, ethoxycarbonylphenylthio, benzylthio, cyanobenzylthio, carboxybenzylthio, fluorobenzylthio, chlorobenzylthio, methylbenzylthio, trifluoromethylbenzylthio, methoxybenzylthio, difluoromethoxybenzylthio, trifluoromethoxybenzylthio, methoxycarbonylbenzylthio, ethoxycarbonylbenzylthio, phenylethylthio, phenylamino, cyanophenylamino, carboxyphenylamino, nitrophenylamino, fluorophenylamino, chlorophenylamino, bromophenylamino, methylphenylamino, trifluoromethylphenylamino, methoxyphenylamino, difluoromethoxyphenyl amino, trifluoromethoxyphenylamino, methoxycarbonylphenylamino,amino,amino, cyanobenzylamino, carboxybenzylamino, fluorobenzylamino, chlorobenzylamino, methylbenzylamino, trifluoromethylbenzylamino, methoxybenzylamino, difluoromethoxybenzylamino, trifluoromethoxybenzylamino, methoxycarbonylbenzylamino, ethoxycarbonylbenzylamino, phenylethylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, n-, i-, s- or t-butylsulphonylamino, N,N-(bis-methylsulphonyl)-amino, N,N-(bis-ethylsulphonyl)-amino, N-methylsulphonyl -N-ethylsulphonyl-amino, N-methylsulphonyl-N-propylsulphonyl-amino, N-acetyl-N -methylsulphonylamino, N-acetyl-N-ethylsulphonylamino, N-propionyl-N -methylsulphonyl-amino, N-propionyl-N-ethylsulphonyl-amino, N-n-butyroyl-N -methylsulphonyl-amino, N-n-butyroyl-N-ethylsulphonyl-amino, N-i-butyroyl-N -methylsulphonyl-amino, N-i-butyroyl-N-ethylsulphonyl-amino, N-n-valeroyl-N -methylsulphonyl-amino, N-n-valeroyl-N-ethylsulphonyl-amino, N-i-valeroyl-N -methylsulphonyl-amino, N-i-valeroyl-N-ethylsulphonyl-amino, N-s-valeroyl-N -methylsulphonyl-amino, N-s-valeroyl-N-ethylsulphonyl-amino, N-t-butyl-carbonyl-N -methylsulphonyl-amino, N-t-butyl-carbonyl-N-ethylsulphonyl-amino, N-benzoyl-N -methylsulphonyl-amino, N-benzoyl-N-ethylsulphonyl-amino.
Group 2 
R2 has, for example, the meanings given above in Group 1.
Group 3 
R2 has, for example, the meanings given above in Group 1.
Group 4 
R2 has, for example, the meanings given above in Group 1.
Group 5 
R2 has, for example, the meanings given above in Group 1.
Group 6 
R2 has, for example, the meanings given above in Group 1.
Group 7 
R2 has, for example, the meanings given above in Group 1.
Group 8 
R2 has, for example, the meanings given above in Group 1.
Group 9 
R2 has, for example, the meanings given above in Group 1.
Group 10 
R2 has, for example, the meanings given above in Group 1.
Using, for example, methyl 3-amino-crotonate and 2,5-difluoro-4-trifluoromethyl-phenyl isocyanate as starting materials, the course of the reaction in the process according to the invention can thus be illustrated by the following scheme: 
The formula (II) provides a general definition of the aminoalkenoic esters to be used as starting materials in the process according to the invention for preparing compounds of the formula (I). In the formula (II), R3 and R4 preferably or in particular have those meanings which have already been indicated above, in connection with the description of compounds of the formula (I)-according to the invention, as being preferred or as being particularly preferred for R3 and R4.
The starting materials of the formula (II) are known and/or can be prepared by known processes (cf. J. Heterocycl. Chem. 9 (1972), 513-522).
The formula (III) provides a general definition of the p-trifluoromethylphenyl isocyanates further to be used as starting materials in the process according to the invention for preparing compounds of the formula (1). In the formula (111), R1 and R2 preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1 and R2.
The starting materials of the formula (III) are known and/or can be prepared by known processes (cf. EP 246061).
The p-trifluoromethylphenyl isocyanates of the general formula (III) are obtained when p-trifluoromethylanilines of the general formula (V) 
in which
R1 and R2 are each as defined above
are reacted with phosgene in the presence of a diluent, such as, for example, chlorobenzene, at temperatures between xe2x88x9220xc2x0 C. and +150xc2x0 C. (cf. also, for example, EP 648749).
The formula (IV) provides a general definition of the p-trifluoromethylphenylurethanes optionally to be used as starting materials in the process according to the invention. In the formula (IV), R1 and R2 preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1 and R2; R preferably represents C1-C4-alkyl, phenyl or benzyl, in particular methyl or phenyl.
The starting materials of the formula (IV) have hitherto not been disclosed in the literature; as novel compounds, they also form part of the subject-matter of the present application.
The novel p-trifluoromethylphenylurethanes of the general formula (IV) are obtained when p-trifluoromethylanilines of the general formula (V) 
in which
R1 and R2 are each as defined above
are reacted with chlorocarbonyl compounds of the general formula (VI)
ROxe2x80x94COxe2x80x94Clxe2x80x83xe2x80x83(VI)
in which
R is as defined above,
if appropriate in the presence of an acid acceptor, such as, for example, pyridine, and
if appropriate in the presence of a diluent, such as, for example, methylene chloride, at temperatures between xe2x88x9220xc2x0 C. and +100xc2x0 C. (cf. the preparation examples).
Suitable reaction auxiliaries for the process according to the invention for preparing the compounds of the formula (I) are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-propoxide, sodium n-, i-, s- or t-butoxide or potassium n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl -dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl -piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN) or 1,8 diazabicyclo[5,4,0]-undec-7-ene (DBU).
Suitable diluents for carrying out the process according to the invention are in particular inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N -dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0xc2x0 C. and 200xc2x0 C., preferably between 10xc2x0 C. and 150xc2x0 C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressurexe2x80x94generally between 0.1 bar and 10 bar.
For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively large excess. The reaction is generally carried out in a suitable solvent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for a number of hours at the required temperature. Work-up is carried out by customary methods (cf. the preparation examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindemia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum
Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and open spaces with or without tree plantings. Equally, the compounds can be employed for the control of weeds in perennial crops for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre-emergence and postemergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
If the extender used is water, it is also possible to employ for example organic solvents as auxiliary solvents. Suitable liquid solvents are essentially the following: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates;. suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For the control of weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlomitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop(-ethyl), flamprop(-iso-propyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-iso-propylammonium), halosafen, haloxyfop (-ethoxyethyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metsulfuron(methyl), metribuzin, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and. 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.